Functionalized Silver-Ion-Mediated α-dC/β-dC Hybrid Base Pairs with Exceptional Stability: α-d-5-Iodo-2′-Deoxycytidine and Its Octadiynyl Derivative in Metal DNA

Silver-mediated α-dC–Ag⁺–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong T_m increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag⁺–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology.     

Exploring the Effect of Ligand Structural Isomerism in Langmuir–Blodgett Films of Chiral Luminescent EuIII Self‐Assemblies

Here we have investigated the influence of the antenna group position on both the formation of chiral amphiphilic Eu^III‐based self‐assemblies in CH₃CN solution and, on the ability to form monolayers on the surface of quartz substrates using the Langmuir–Blodgett technique, by changing from the 1‐naphthyl ( 2(R) , 2(S) ) to the 2‐naphthyl ( 1(R) , 1(S) ) position. The evaluation of binding constants of the self‐ assemblies in CH₃CN solution was achieved using conventional techniques such as UV/Visible and luminescence spectroscopies along with more specific circular dichroism (CD) spectroscopy. The binding constants obtained for EuL , EuL₂ and EuL₃ species in the case of 2‐naphthyl derivatives were comparable to those obtained for 1‐naphthyl derivatives. The analysis of the changes in the CD spectra of 1(R) and 1(S) upon addition of Eu^III not only allowed us to evaluate the values of the binding constants but the resulting recalculated spectra may also be used as fingerprints for assignment of the chiral self‐assembly species formed in solution. The obtained monolayers were predominantly formed from EuL₃ (≈85 %) with the minor species present in ≈15 % EuL₂ .     

Synthesis and characterization of MIIU3O10 · nH2O (MII = Mg, Mn, Co, Ni, Cu, Zn, Cd) triuranates

Individual crystalline phases of composition M^IIU₃O₁₀ · nH₂O were prepared by reacting schoepite UO₃ · 2.25H₂O with aqueous solutions of Mg, Mn, Co, Ni, Cu, Zn, or Cd nitrates under hydrothermal conditions at 200°C. The composition and structure of the resultant compounds were determined by hightemperature X-ray diffraction, IR spectroscopy, scanning calorimetry, and chemical analysis; the dehydration and thermal destruction of the compounds were studied.     

State of uranyl silicates MII(HSiUO6)2 ·6H2O (MII=Mn, Co, Ni, Cu, Zn) in aqueous solutions

Uranyl silicates with formula M^II(HSiUO₆)₂·6H₂O (M^II=Mn, Co, Ni, Cu, Zn) were investigated in aqueous solutions in the pH range of 0÷14. The pH interval was established where compounds preserve their composition and structure. It varies in the pH range of (3.5–4.0)÷(10.8–11.4) and depends on M^II type. Out of this pH interval investigated uranyl silicates convert to the compounds of other composition and structure, such as amorphous silica, polyuranates and hydroxides of 3d-transition elements. The solubility of M^II(HSiUO₆)₂·6H₂O was determined, it’s value changes on the several orders of magnitude from 10^?6 M in subalkali solutions to 10^?3 M in acid and strongly alkaline media. Using obtained experimental data the solubility products and solubility curves of uranyl silicates were calculated by mathematical modeling. Also the speciation diagrams of uranium (VI), silicon (IV) and M (II) in solutions and solids were plotted.     

Synthesis,Structure, and Properties of Cesium Polyuranate [Cs2(H2O)3][(UO2)6O3(OH)8]·2H2O

Russian Journal of General Chemistry - Cesium uranate [Cs2(Н2О)3][(UO2)6O3(OH)8]·2H2O was obtained by reacting hydrated uranium(VI) oxide UO3·2.25H2O with a cesium nitrate...     

Director configurations in nematic droplets with tilted surface anchoring

The polymer dispersed nematic liquid crystal (LC) with the tilted surface anchoring has been studied. The droplet orientational structures with two point surface defects – boojums and the surface ring defect – are formed within the films. The director tilt angle α = 40° ± 4° at the droplet interface and LC surface anchoring strength W_s ~ 10^–6 (J m^?2) have been estimated. The bipolar axes within the studied droplets of oblate ellipsoidal form can be randomly oriented are oriented randomly relatively to the ellipsoid axes as opposed to the droplets with homeotropic and tangential anchoring.     

Estimation of protein folding rate from Monte Carlo simulations and entropy capacity

The problem of protein self-organization is one of the most important problems of molecular biology nowadays. Despite the recent success in the understanding of general principles of protein folding, details of this process are yet to be elucidated. Moreover, the prediction of protein folding rates has its own practical value due to the fact that aggregation directly depends on the rate of protein folding. The time of folding has been calculated for 67 proteins with known experimental data at the point of thermodynamic equilibrium between unfolded and native states using a Monte Carlo model where each residue is considered to be either folded as in the native state or completely disordered. The times of folding for 67 proteins which reach the native state within the limit of 10(8) Monte Carlo steps are in a good correlation with the experimentally measured folding rate at the mid-transition point (the correlation coefficient is -0.82). Theoretical consideration of a capillarity model for the process of protein folding demonstrates that the difference in the folding rate for proteins sharing more spherical and less spherical folds is the result of differences in the conformational entropy due to a larger surface of the boundary between folded and unfolded phases in the transition state for proteins with more spherical fold. The capillarity model allows us to predict the folding rate at the same level of correlation as by Monte Carlo simulations. The calculated model entropy capacity (conformational entropy per residue divided by the average contact energy per residue) for 67 proteins correlates by about 78% with the experimentally measured folding rate at the mid-transition point.     

Effect of matrix domination in PANI interpolymer complexes with polyamidosulfonic acids

Various polyaniline (PANI) interpolymer complexes with polyacids in the form of molecular solutions were synthesized by chemical oxidative polymerization of aniline in the presence of water-soluble poly-(2-acrylamido-2-methyl-1-propanesulfonic acid) (flexible backbone), poly-p,p′-(2,2′-disulfoacid)-diphenylene-terephthalamide (t-PASA, rigid backbone), and their mixtures in different ratios. The complexes were characterized by UV-Vis-near infrared spectroscopy in solutions; also, the films’ drop-casts from these solutions were investigated by cyclic voltammetry, spectroelectrochemical, direct current (DC) conductivity, and atomic force microscopy (AFM) measurements. It was shown that the nature of polyacid affects the shape of spectra and the dynamics of their changes. The character of spectral changes during the matrix synthesis of PANI in the presence of mixtures of the rigid-chain and flexible-chain matrixes and the study of spectral properties of the obtained PANI solutions demonstrates the existence of the rigid-matrix domination effect in the process of formation of PANI interpolymer complexes. Spectral properties of the obtained PANI complexes with the mixtures of flexible-chain and rigid-chain polyacids of different ratios (3:1, 1:1, 1:3, and 1:6) are very similar to those ones for the complex with rigid-chain t-PASA. At the same time, there is a correlation between the electrical conductivity and morphology of the films of PANI complexes and their composition, the conductivity passing through a minimum for the complexes with the polyacid mixtures (6:1, 3:1, and 1:1).